Polyazo dyestuffs



Patented Feb. 20, 19401 TED STATES 2,190,750 POLYAZO DYESTUFFS Paul Zervas, Cologne-Mulheim, Germany, assignor to General Aniline & Film Corporation, a, corporation of Delaware No Drawing, Application August 23, 1938, Serial No. 226,247. In Germany August 27, 1937 40mm. (01. zeal-16s) i *"I'he present invention relates to new polyazo ,dyestuifs andto a method of preparing the same;

moreparticularly it relates to polyazodyestufis containing two azo groups in peri-position.

"Azo dyestufis bearing two azo-bridges in periposition have hardly been prepared and investigated as to their usefulness until now. In Helv. chim, acta XV, 1932, pages 110 and 1342,Ruggli and coworkers describe simple representatives of They couple 2.7-dihydroxynaphthalene "twice with energetically coupling,

this dyestuif-class.

diazo compounds; besidesthey couple p-aminobenzene-sulfonic acid or aminobenzene in an alkaline solutionwith l-amino-V-hydroxynaphthalene, further diazotize this peri-aminoazodyestuir and then couple with B naphthol or 1.3-dihydroxybenzene. In this way they obtain perif disazo dyestuffs the constitution of which is proved by splitting up the dyestuffs. Likewise azodyestuifs without salt-forming, groups are described in German Patent 432,426 which are indirectly developed on the fiber to peri disazo dyestuifs. i v

It has now been found that valuable polyazo dyestuffs which bear azo groups in peri-position are obtained, if peri-disazo dyestuffs being further disazotizable or perisaminoazo dyestuffs are prepared by coupling I -amino orIZ-aminofl-v hydroxynaphthalenes which in the first case may i contain any azo-residue in l-position and in each case a watersolubilizing group withsuitable diazoj components in ,8-position or in 1- and S-position or in the case of the 1-amino 'l-hydroxynaphthalene also by first diazotizing the amino group, combining with a middle or final component, and only then coupling into the 8-position, ;and'if these peri-disazoor peri-aminoazo dyestuffsafter reduction, saponification or treatment with phosgene if this should be necessary or desired-- are diazotized or tetrazotized, as the case may, be, and combined with m-diamino-, hydroxyor m-dihydroxycompounds of the benzeneseries or the derivatives or the substitution products thereof,capable of coupling;: i

The manufacture of these new polyazo dyestuffs can accordingly take place by using c. g.

1-amino-7-hydroxynaphthalene as starting ma terial, combining this in an acid solution with a diazo compound, coupling the dyestuffthus obtained in an alkaline solution with a saponifiable diazo compound, e. g. with formyI-L3-diaminobenzene, saponifying this peri-aminodisazo dyestuff, tetrazotizing and combining with a final component. Furthermore an l-amino-fl-hydroxynaphthalene sulfonic acid can be employed; it is coupledin analkaline medium with a saponifiable diazo compound, the dyestuif obtained is saponified and, as described above, further tetra zotized and coupled. On the other hand it is possible to diazotize first l-amino-fl-hydroxynaphthalene or its sulfonic acids, if desired in the form of theiraryl sulfonic acid esters, to combine this diazo compound with anlaminocompoundg or final component capable of coupling, if neces sary to saponify the dyestufi, to treat it with phosgene if desired, then to couple in an alkaline medium, to saponify again if necessary, to diazotize or tetrazotize, as the case may be, and so on.

Moreover it is possible to start from 2-amino-7- hydroxynaphthalene or its sulfonic acids, couple these twice--once in acid and once in alkaline solution -with a diazo compound, and then to convert the peri-disazo dyestuff into a polyazo dyestuif in the'manner described above.

I My new azo dyestuifs correspond to the general X 1 In this formula A stands for the residue of an azo dyestufi which contains as final component m-diaminobenzne, hydroxybenzene or m-dihydroxybenzene or the substitution products 01" derivatives thereof, B stands for one of the above named final components, namely m-diaminobenzene, hydroxybenzene, m-dihyolroxyben-v zene, the nuclear substitution products or the' derivatives thereof, or for an azo dyestufi. residue; which contains these compounds as final components, X stands stands either for hydrogen, -SO3l-I or the radical -N=N-R, wherein R represents the radical of an aromatic The azo dyestuff residues designated A andB in the above formula can be built up from benit is to be understood that the term benzenealso includes diphenyl and that whenever-theabove components of the azo dyestufi residues are mentioned also their N-aminobenzoylatedcompounds and ureas shall be included and, of course, also their usual substitution products; The final comthese azo dyestufi residues, the

ponents of m-diaminobenzenes, hydroxybenzenes and m-dimay further be substituted i by hydroxy-alkyl, carboxy-allgyl or siflfo-alkyl radicals. The radical --N=N-R is the radicalv 01 a 'diazo compound derived from amino compounds of benzene, diphenyl, naphthalene and of.

sulfonic acids thereof; these amines may be substituted in the nucleusby N02, halogen, alkyl, alkoxy and the acetamino group. The number compound, Y stands for hydrogen or the amino group, and n stands forawhole number. i

. zene, naphthalene and phenylpyrazolone radicals;

of sulfonic acid residues present inthe dyestuff molecule is usually one or two, but since the water-solubility of the dyestuffs depends on the:

presence of SOsH groups their number will increase with increasing size of the dyestuff' molecule. v

Thenew watersoluble polyazo dyestuffs dye vegetable fibers directly and can, according. to the final component, be developed with p-nitrodiazobenzene, ,B-naphthol etc. or after-treated with copper or chromium salts. All these dyeings are distinguished-While otherwise; showing the same good properties--over similar dyestuffs which bear only one or no azo-bridge in peri-position, by a remarkably improved fastnessto light. The followingexamples illustrate the inventionpwithout, however, restricting it thereto, the

parts being by weight.

" Example 1 v 13.6 parts of formyl-1.3-diaminobenzene are stirred into GOparts of cold water, dis-solved by adding 28 parts of hydrochloric acid (sp. gr. 1.15)

and thereto at a temperature of 0 C. a solution of 6 .9 parts of sodium nitrite is added; The diazo solution is run into a solution. of 23.9 parts of l-amino-7-hydroxynaphthalene-3-sulfonic acid 1 in the presence of 28 parts of sodium carbonate f at a temperature of 0-2" C. After finishing the coupling the dyestuff solution is mixed with-135 parts of sodium hydroxide solution (sp. gr. 1.36) and heated for 2 hours to a temperature outdo-4:5 I

C. in order to saponify the formyl group." 'By adding 150 partsof hydrochloric acid (sp. gr. 1.15) the dyestuff is'separated and isolated. The dyestuff paste is dissolved in about 1200 parts of water'and some sodium hydroxide solution, 15

parts of sodium nitrite and 70 parts of hydro chloric acid (sp. gr.1.'15 are added at 0 C .,and indirectly tetrazotized for one to two hours. Whenthe.tetrazotization is finished the excess of nitrite is destroyed with some amino sulfonic acid and a solution of 21.6 parts of lB-diaminobenzene is added. By slowly adding a solution of parts of sodium acetate the coupling is brought to an endwithin about 6 hours. Then the mix "ture isne'utralized by adding sodium carbonate 1 solution and theformed dyestuff is isolated. It

represents in dry form a dark powder which' is easily soluble in water and dyes cotton yellowish I brown shades. By after treatmen't with n-nitroobtained. The dyestuff hasin the free state the a diazobenzene a reddish-brown fastto light is following constitution:

NH: &

Example2 v39.3 parts of l-amino-l-(p-toluenesulfonyl)- hydroxymaphthalene-bsulfonic .acid. are dissolved in 700' parts of water and by adding 28 parts of hydrochloric acid, (sp. gr. 1.15) and at 22-25 C. a solution of 6.9 parts of sodium nitrite diazotized. Diazotization takes about 2 hours. Then 10.? parts of3-amino-1-methylbenzene, dissolved in little water and 14 parts of hydrochloric acid made complete within 24 hours by gradually adding a-solution of 15 parts of sodium acetate. The

isolated dyestufl paste, is stirred into 500 parts of water. mixed with 250 parts of sodium hydroxide solution (sp. gr. 1.36) and heated for three hours up to -85" CI; when the saponification is com- 7 plete a reddish-brown solution results. By add- -.in.g 250 parts of hydrochloric acid (sp. gr. 1.19)

the dyestuff is precipitated and then sucked off. Thedye'stuii paste is dissolved in about 800 parts of water and some-sodium carbonate and combinedin the presence of 28 parts of sodium carbonate with a diazo solution of 13.6 parts of iormy1 1.3-diaminobenzene, obtained according to Example 1, at a temperature of -5 C. to- 2? C. When the coupling iscoinplete' parts ofv sodium hydroxide solution (sp. gr. 1.36) are added 7 and heated for 2 hours to 60 C. The saponified dyestufi is precipitated byadding parts of hydrochloric acidlspgr. 1.19) and isolated. The

dyestuff paste is dissolved, sodium carbonate being added, tetrazotized according to Examplel andpoupled with 21.6 parts of 1.3-diaminobenzene. The isolated dyestuff. dyes cotton directly (sp. gr. 1.15) are added. The coupling is.

reddish brown shades, which change into a beautiful browniast to .light, when treated with p-- nitrodiazobenzene. -The dyestuff corresponds in the free state to the following formula;

Q =N .N- N=N HO I NH2 1.1

i 1. NIL-O" SOsH I NH: I

' Example 3 The dyestuff paste obtained according to Example 2 by coupling the diazo compound of 39.3

parts of 1-amino-7- (p-toluenesulfonyl) yd.roxy- -naphthalene'-sulfonic.acidwith- 10.7 parts of '3.-ami no-l-methylbenzene and". saponifying is treatedin a solutionrendered alkaline by sodium carbonate with phosgene at .60.C. When the I treatment with phosgene' is finished the precipitated. dyestufi is'isolated and, as, described in Examples 1 and 2, coupled in sodium carbonate v alkaline solution with a diazo solution of 13.6

parts. of 'formyl-1.3-diamino-benzene, saponified. tetrazotized and combined.with.21.6 parts of 1.3 diaminobenzene. The dyestuif represents a dark powder and dyes cotton reddish-brown shades and yields; when developed." brown shades. The

dyestufl corresponds in the free state to the following .iormula: v

HIN

NH, V 2

' Example 4 15.9 parts of .1-amino-7-hydroxynaphthalene are dissolved in 14 parts of hydrochloric acid formedis isolated. The dyestufi paste is dis solved in 2000 parts of water and combined in the presence of 28 parts of sodium carbonate with a diazo solution of 13.6 parts of formyl-1.3- diaminobenzene at 3-5 C. When the coupling is complete the mixture is saponified by adding 180 parts of sodium'hydroxide solution (sp. gr. 1.36) and heating to 40 C. for 2 hours, made acid to Congo redpaper by adding 250 parts of hydrochloric acid (sp. gr. 1.19), and the dyestufiis isolated. The dyestuff paste is suspended in 3000 parts of water, rendered just alkaline with sodium hydroxide solution and indirectly diazotized by adding 500 parts of ice, 15 parts of sodium nitrite and 150' parts of hydrochloric acid (sp. gr. 1.19) for two hours at 3-5 C. After destroying the excess of nitrous acid a solution of 10.8 parts of 1.3-diaminobenzene and 18.8 parts of 1.3-diaminobenzene-4-sulfonic acid are added to the diazotization mixture. By adding drop by drop a solution containing 60 parts of sodium carbonate the coupling is finished. The isolated dyestuff represents a dark powder, which dyes cotton yellowish brown shades and yields a full brown when treated with p-nitrodiazobenzene. The dyestuif corresponds in the free state to the following formula:

N==N NE:

If in this example the p-aminobenzene sulfonic acid is replaced by mor o-aminobenzene sulfonic acid or by an acetylphenylene diamine sulfonic acid or by an aminonaphthalene sulfonic acid dyestulfs of similar properties are obtained.

Example 5 dium carbonate alkaline medium. The dyestufi isisolated by adding salt and represents a brown powder, which dyes cotton reddish-brown shades yielding a yellowish-brown when after-treated with-chromium'salts. It corresponds in the free state to the following formula:

COOH 0 Example 6 41.6 parts of the dyestufi from diazotized formyl-1.3-diaminobenzenei-sulfonic acid and 1- (4-aminophenyl) -3-methyl-5-pyrazolone are indirectly diazotized in the usual manner, combined with 23.9 parts of 1-amino-7-hydroxynaphthalene-4-sulfonic acid in alkaline medium and, when the coupling is complete, saponified by adding sodium hydroxide solution and heating to 40 C. The isolated dyestuff is tetrazotized according to Example 4 and is. coupled witha solution of 30.4 parts N-hydroxyethyl-L3-diaminobenzene The dyestuff dyes cotton yellowish-brown shades and is developed to a redbrown by aftertreatment with p-nitrodiazobenzene. It corresponds in the free state to the following formula:

HO: S 0311 Nmomcmon Example 7 39.3 parts of 1-amino-7- (p-toluenesulfonyl) hydroxynaphthalenel-sulfonic acid are diazotized according to Example 2, mixed with a hydrochloric solution of 12.2 parts of 2.4-diaminol-methylbenzene, and the beginning coupling is made complete by gradually adding sodium acetate solution. The isolated dyestufi is saponified in the usual manner by heating it to 80 C. in sodium hydroxide alkalinesolution and precipitated from the solution by adding hydrochloric acid. The dyestufi paste is stirred into 1500 parts of water, rendered alkaline and combined with the coupling product obtained from the tetrazo compound of 18.4parts of 4.4'-diaminodiphenyl (0.1 mol) and 13.8 parts of l-hydroxybenzene-2-carboxylic acid (0.1 mol). The formed dyestuif is precipitated by adding salt and isolated; it dyes cotton yellowish-brown shades of good fastness to light and corresponds in. the free state to the following formula: 1

OOOH

SOaH If in this example the coupling product obtained from 0.1 mol tetrazotized benzidine and 0.1 mol salicylic acid is replaced by the coupling product obtained from 0.1 mol tetrazotized p-aminobenzoyl-p-phenylenediamine and 0.1 mol salicylic .lOl

' solution obtained from 13.6 parts of formyl-l3- diaminobenzene.

When the coupling is complete the formed diazo dyestufi is saponified accordingtoExample l, indirectly tetrazotized and coupled with amixture of 10.8 parts of l.3-diaminobenzene and 16.6 parts of m-aminophenyb glycine. The isolated dyestuff dyes cotton, when aftertreated with penitrodiazobenzene, reddishbrown shades of good fastness properties. It corresponds in the free state to the following formula HQN- N=N H0 NHz N=NQNH2 NH H038 )NHQ *ontooon,

Example 9 The tetrazo compound of the saponified dyestuff obtained from 13.6 parts of formly-1.3- diaminobenzene and 23.9 parts of l-amino ihydroxynaphthalene-3-sulfonic acid according to Example 1 is combined with 22 parts of 1.3-dihydroxybenzene. The coupling and isolation of the dyestufi takes place according to- Example 1. The dyestuif dyes cotton reddish-brown shades. When aftertreated with p-nitrodiazobenzene a yellowish-brown shade is obtained. The-dyestuff corresponds in the free state to the following formula:

I claim:

1. As new products Water-soluble substantive 0 polyazo'dyestufls of the general formula:

wherein A and B stand for radicals offinal components selected from the" group consisting of m diaminobenzene, hydroxybenzene, m-dihydroxybenzene, the alkyl, halogen, N02, SOsH, COOH nuclear substitution products thereof and the N-hydroxyalkyl--, ,N-carboxyalkyl-, 'N-sulfoalkyl-derivatives 0f the said diamines, R1 stands for one of the group-consisting of monocyclic and bicyclic aromatic radicals, R2 stands for one of the group consisting of the benzene nucleus, of alkyl substituted and alkoxy substituted benzene nuclei, Y stands for a member selected from the group consisting of hydrogen and NH2, and n stands for one of the values 1 and 0.

2. As new products water-soluble substantive HO Y wherein A and B stand for radicals of final components, selected from the group consisting of m-diaminobenzene, hydroxybenzene, .in-dihy droxybenzene, the alkyl, halogen, N02, SOsI-I, COOl-I nuclear substitution products thereof and the N-hydroXyalkyl-, Ncarboxyalkyl- ,N-sulfoalkyl-derivatives of the said. diamines, a1 stands for a benzene radical, R2 stands for one of the group consisting of the benzene nucleus, of alkyl substituted and alkoxy substituted benzene nuclei. Y stands for a member selected from the group consisting of hydrogen and NH2, and it stands for one of the values 1 and 0.

3. As new product the watersoluble substantive polyazo dyestuff corresponding in its free state to the formula:

dyeing cotton directly reddish-brown shades which change into a beautiful brown fast to light when aftertreated with p-nitrodiazobenzene.

4. As new product the watersoluble substantive polyazo dyestufi? corresponding in its free state to the formula:

OOOH N112 dyeing cotton directly yellowish-brown shades of good fastness to light.

I PAUL ZERVAS 

